Process for treatment of aqueous soluions of polyhydric alcohols

ABSTRACT

The process relates to the treatment of aqueous solutions of polyhydric alcohols to remove heavy metal components, oils, organic contaminants and, optionally, water. The process is particularly well suited for use in the treatment of spent antifreeze/coolant from the cooling systems of internal combustion engines.

FIELD OF THE INVENTION

The instant invention relates to a process for the treatment of aqueoussolutions of polyhydric alcohols, e.g. ethylene glycol, containingcontaminant(s), particularly a heavy metal such as lead, copper, iron,zinc and non-heavy metals such as aluminum. The instant invention isparticularly useful in treatment of an antifreeze/coolant removed fromheat exchange systems, including those of automobiles and trucks.

INFORMATION DISCLOSURE STATEMENT

Considerable interest has been associated with the purification ofnumerous polyhydric alcohols in relation to their manufacture. Inparticular, the purification of aqueous ethylene glycol has receivedconsiderable attention owing to the commercial significance of ethyleneglycol in the manufacture of polyester.

U.S. Pat. No. 3,732,320 discloses a purification process for reducingthe iron content of ethylene glycol from an ethylene glycolmanufacturing process. The process involves contacting ethylene glycolwith a cation exchange resin in the acid cycle. Although the removal ofiron was of primary concern to the patentee, the patentee generallystates that "iron and other metallic contaminants present in traceamounts" may be removed by the cation exchange treatment.

U.S. Pat. No. 4,118,582 discloses a recovery process for removingdissolved antimony catalyst from unreacted ethylene glycol recoveredfrom the manufacture of polyester. The recovery process involves a pHadjustment of the spent glycol to about 2 to 7, reaction with an alkalimetal borohydride to form a metallic antimony precipitate, separation ofthe metallic antimony precipitate from the spent glycol (unreactedethylene glycol from the manufacture of polyester) in the absence ofoxygen, followed by distillation of ethylene glycol from the spentglycol.

U.S. Pat. No. 4,260,827 discloses a process for the purification ofaqueous solutions of low molecular weight polyhydroxyl compounds. Thepatentee's process is directed to the purification of low molecularweight polyhydroxyl compounds after their manufacture in the presence ofcatalysts containing calcium and/or lead. The patentee's processinvolves numerous treatment and distillation steps. The aqueous solutionof the low molecular weight polyhydroxyl compound is first treated withmethanol and a precipitant to form a precipitate to be separated from aresidual solution. The pH of the methanol/precipitant solution of lowmolecular weight polyhydroxyl compounds may be adjusted to a pH from 1to 4 to maximize precipitation of the calcium and/or lead compounds fromthe methanol treated solution. The deposits (precipitates) are removedby filtration and the residual solution treated with a cation exchanger.The residual solution is then distilled to remove low-boiling fractions.The distillation sump essentially containing the low molecular weightpolyhydroxyl compounds is then treated with an anion exchanger.

The above processes have been directed to manufacturing processes wherea manufactured product is being purified or where there is a need topurify and recover unreacted raw materials from specific reagentspresent as a result of commercial processes. Such processes deal withpurification of compositions with limited and well understoodcontaminants.

The purification of more ethylene glycol-containing streams fromautomotive cooling systems raises significantly more complex questionsas to the contaminants to be removed by treatment. For example, thepurification of a spent antifreeze/coolant is a dramatically differenttreatment process owing to the novel and harsh environment to which theantifreeze/coolant has been subjected and, further, owing to thespecific and unique chemical components commonly present in the spentantifreeze/coolant to be treated. Owing to the complexities associatedwith treating a spent antifreeze/coolant it is not surprising that fewattempts have been made to treat spent antifreeze/coolant solutions.

U.S. Pat. No. 4,791,890 discloses a flushing process employing aflushing liquid having entrained gas bubbles) for an automotive coolingsystem wherein the patentee includes a filtering step (at 302). Thepatentee provides no other treatment of the spent antifreeze coolant.U.S. Pat. No. 4,793,403 discloses a coolant system for use in treatmentof coolant liquid. The liquid coolant is treated by filtering to removecontaminant from the coolant liquid. The patentee discusses a chemicaltreatment at column 3, lines 11 to 28, but only in vague terms and onlyby addition of chemical components previously present in the originalantifreeze/coolant, i.e., addition of new additives. The patenteediscloses removal of particulate and congealed substances through afilter (28) followed by treatment of aqueous liquid by addition ofchemical agent or agents. The patentee does not disclose any particulartreatment, merely alluding to the fact that such chemicals can includecorrosion inhibitor, i.e., anti-rust compound, pH adjustment chemicals,and fresh antifreeze compound (glycol, for example). In addition, atcolumn 3, lines 38 to 48, filter 41 may contain "metal powder" toprovide metallic ions for neutralizing electrical charge. Similarly,Kleer-Flo Company has published the details of a antifreeze recyclemachine (Kleer-Flo® AF 250 Anti-Freeze Recycler) which employs a threestep filtration system which employs a stainless steel screen filter, apre-filter for removing materials down to a size of 5 microns and athird filter alleged to remove impurities at the molecular level(approximately 50 Angstoms). After filtration the filtered antifreeze ismixed with an additive package to provide a working antifreeze forreintroduction into an automotive cooling system. No chemical removalprocess is disclosed whereby the purification of the spentantifreeze/coolant is achieved.

The above discussion of the prior art demonstrates the failure of theprior art to disclose an effective process for the purification of usedethylene glycol-based heat exchange fluids, particularly used spentantifreeze/coolant from automotive cooling systems. It is particularlyuseful to note the lack of effective treatment steps of the spentantifreeze/coolant in U.S. Pat. No. 4,793,403 and by the Kleer-Flo® AF250 Anti-Freeze Recycler for contaminants such as heavy metals andorganic compounds other than ethylene glycol. Further, such processesspecifically warn against their use when the spent antifreeze/coolant tobe treated contains an oil component. Such a limitation of usesignificantly detracts from the commercial use of such processes.

SUMMARY OF THE INVENTION

The instant process relates to the treatment of aqueous polyhydricalcohol-containing compositions. In one embodiment the polyhydricalcohol containing compositions are from a heat exchange system of aninternal combustion engine which typically contains between about 5weight percent and about 95 weight percent ethylene glycol, and containsat least one metal, typically a heavy metal, and/or an oil component tobe removed.

The instant process generally comprises steps of:

(i) adjusting the pH of said polyhydric alcohol-containing compositionto between about 4.0 and about 7.5 by addition of an effective amount ofan pH adjusting agent to form a pH-adjusted composition;

(ii) adding an effective amount of a precipitating agent for at leastone metal, preferably at least one heavy metal, and/or oil componentpresent in the pH-adjusted composition; and

(iii) preferably also includes adding to the pH-adjusted composition ofstep (ii) an effective amount of a coagulating agent and an effectiveamount of a flocculating agent effective in forming a precipitatecontaining at least one metal; and

(iv) passing the pH-adjusted composition through a first filtrationmeans to remove a major amount of said metal-containing precipitate and,optionally, physical skimming of the surface of said pH-adjustedcomposition to remove precipitate at said surface.

In addition to the above steps the instant treatment process may alsoinclude one or more of the following steps:

(v) passing the pH-adjusted composition from the first filtration meansthrough a second filtration means effective in the physical separationof particles of a smaller size that said first filtration means;

(vi) passing the pH-adjusted composition after the second filtrationmeans through an organic separation means effective in removing organiccompounds (other than the polyhydric alcohol(s)) from the pH-adjustedcomposition;

(vii) passing said pH-adjusted composition through a third filtrationmeans having an effective physical separation of particles by sizesmaller than said second filtration means; and

(viii) passing said pH-adjusted composition after filtration through anion exchanger anion and/or cation effective in the removal of at leastone solubilized metal, preferably heavy metal, from said pH-adjustedcomposition.

DETAILED DESCRIPTION OF THE INVENTION

At the outset it is important to note that although the instantinvention is primarily directed to the treatment of spentantifreeze/coolant from the heat exchange systems (commonly referred toas "cooling systems") of internal combustion engines, the process of theinstant invention is useful in purifying a wide range of contaminatedaqueous ethylene glycol composition.

The term "heat exchange system" is employed herein to include any heatexchange system and includes cooling systems for internal combustionengines, as commonly employed in automobiles, trucks, motorcycles,airplanes, trains, tractors, generators, compressors and the like. Thecooling system in automobiles and trucks are representative of such heatexchange systems for internal combustion engines. Automotive heatexchange systems and their construction are well known in the art andare known to contain several metals, including aluminum and lead solderwhich with time may be dissolved into the working antifreeze/coolantcomposition within the cooling system by physical abrasion and/orchemical action. The term "spent antifreeze/coolant" herein refers to anantifreeze/coolant which has operated as the antifreeze and/or coolantfor a time in a heat exchange system, including an automotive coolingsystem.

The term "metals" as used herein in reference to the metal componentspresent in the spent antifreeze/coolant includes metals such as aluminumand magnesium and "heavy metals" such as lead, iron, zinc, manganese,copper and molybdenum. Although aluminum is not a "heavy" metal as thatterm is understood in the prior art, the term "heavy metal" as usedherein is intended to include aluminum as to the metal componentspresent in a spent antifreeze/coolant which are subject to removal bythe instant process. Owing to the construction of a cooling system so asto include aluminum surfaces in contact with a workingantifreeze/coolant, it is common for the spent antifreeze/coolant tocontain aluminum.

The antifreeze/coolant employed in heat exchange systems is generally amixture of an alcohol (including methanol, ethanol, propanol, butanol,ethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, glycerol, butene glycol, the monoacetate of propylene glycol,the monoethylether of glycol, the dimethyl ether of glycerol, alkoxyalkanols and mixture thereof); with the preferred alcohols beingselected from the group consisting of ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol and mixtures thereof, andpreferably consists of ethylene glycol, water and additional chemicalcomponents which provide corrosion protection or other beneficialfunction for the particular heat exchange system(s) wherein it isemployed. Further, it is well known that up to about 10% diethyleneglycol or higher may be present in the grade of ethylene glycol employedto manufacture antifreeze/ coolants for cooling systems.

Owing to the wide spread use antifreeze/coolants in internal combustionengine cooling systems based upon ethylene glycol/water mixtures, theinstant invention is particularly useful in conjunction with ethyleneglycol-based antifreeze/coolants heretofore employed as heat exchangefluids for the cooling systems of internal combustion engines. Suchethylene glycol-based antifreeze/coolants representative of suchantifreeze/coolant compositions are those containing silicone/silicateadditives and/or various carboxylic acids as corrosion inhibitors forthe automotive cooling systems. Other optional additives are typicallyemployed in commercial antifreeze/coolants in minor amounts of less than50 wt. percent based on the weight of the antifreeze/coolant. Typicaloptional additives included in antifreeze/coolants include, for example,known corrosion inhibitors for aluminum or other metals include, forexample, molybdates, mono and/or di-aliphatic acids, e.g., sebacates,carbonates, silicates, alkali metal nitrates, alkali metal nitrites,diisopropylamine nitrite, dicyclohexylamine nitrate, tolyltriazole,mercaptobenzothiazole, benzotriazole, zinc compounds, calcium compounds,phosphates, benzoates, and the like, or mixtures thereof. Further, oneor more of the known inhibitors for various metals are in an "inhibitoryeffective amount", i.e., an amount sufficient to provide a measurableamount of corrosion inhibition with respect to the metal (e.g., copper,steel, brass, aluminum, cast iron, solder, etc.) surfaces to beprotected as compared to the corrosion protection provided by theantifreeze/coolant without these inhibitors. Other optional additivesthat may be present in commercial antifreeze/coolants include: wettingagents and surfactants such as, for example, known ionic and non-ionicsurfactants such as the poly(oxyalkylene) adducts of fatty alcohols;defoamers and/or lubricants such as the well-known polysiloxanes and thepolyoxyalkylene glycols; wear inhibitors, such as the zincdithiophosphates and the zinc thiocarbamates; lubricants, such assilicone pump lubricants; and other ingredients known in the art ofantifreeze/coolants that do not adversely affect the antifreeze/coolantcharacteristics sought to be achieved by the end use of theantifreeze/coolant.

Representative antifreeze/coolant compositions based upon polyhydricalcohols which may be treated according to the instant invention afteruse in a heat exchange system, i.e., when collected after use (e.g., a"spent" antifreeze/coolant from an automotive cooling system) include,but are not limited to, those described in U.S. Pat. Nos. 4,664,833,4,287,077, 4,725,405, 4,704,220, 4,684,474, 4,685,475, 4,687,590,4,701,277, 4,561,990, 4,578,205, 4,584,119, 4,587,028, 4,588,513,4,592,853, 4,629,807, 4,647,392, 4,657,689, 4,759,864, 4,851,145,4,810,406 and 4,345,712; the aforementioned patents incorporated hereinby reference. In the aforesaid patents are disclosed combinations ofchemical components effective in protecting the metal surfaces of suchcooling systems, such being generally referred to as an "inhibitorpackage."

The spent antifreeze/coolant mixtures obtained by removal from heatexchange systems of internal combustion engines are generallycharacterized as containing ethylene glycol or other polyhydricalcohol(s) and are typically a mixture containing between about 95volume percent and about 5 volume percent ethylene glycol and/or otherpolyhydric alcohol, preferably between about 30 volume percent and about70 volume percent. The actual amount of ethylene glycol and/or otherpolyhydric alcohol present in the antifreeze/coolant will depend onseveral factors. For example, during the "change-over" of anantifreeze/coolant in the cooling system of an internal combustionengine the cooling system will be emptied and the removedantifreeze/coolant placed in a collection container. The cooling systemwill typically then be flushed with water and/or water with a minoramount of a cleaning agent. This substantially water solution willtypically be emptied into the same holding container as the originalspent antifreeze/coolant and, thus, further decrease the ethylene glycolconcentration in liquid mixture to be recycled. Further, the spentantifreeze/coolant is typically characterized as containing at least oneheavy metal selected from the group consisting of lead, iron, zinc,manganese, copper, molybdenum, and aluminum and various organic oilsfrom the internal combustion engine or present as a result ofcontamination after removal of the antifreeze/coolant.

The antifreeze/coolant will also typically contain one or more organiccompounds other than the polyhydric alcohol(s) component. Such organiccompounds may be present as a result addition as a functional additiveto the original antifreeze/coolant or may be present as a degradationproduct of the polyhydric alcohol, e.g., ethylene glycol, or otherorganic compound present in the original antifreeze/ coolant. Forexample, it is well known that under the working conditions that anantifreeze/coolant experiences in an automotive cooling system thatthermal degradation of ethylene glycol and other organic compoundspresent in the working antifreeze/ coolant will result in the presenceof organic degradation products. Typical organic degradation products ofethylene glycol include, but are not limited to, formic acid, glycolicacid and acetic acid. Antifreeze/coolants also are known to containinorganic components as corrosion inhibitors including, but not limitedto, silicate, nitrate, nitrite, silicone compounds, phosphate, chloride,sulfate, carbonate and mixtures thereof, and salts commonly found inwater.

Analyses of spent antifreeze/coolants taken from commercialantifreeze/coolant change-over (including flushing liquids, e.g.,water), are set forth in Table A:

                  TABLE A                                                         ______________________________________                                        Component.sup.2                                                                        Low Value.sup.3                                                                          High Value.sup.3                                                                         Average Value.sup.1, 3                         ______________________________________                                        pH       8.5        10.0       9.3                                            Wt. % EG 12.1       40.0       28.8                                           Wt. % DEG                                                                              0.5        3.5        1.37                                           Wt. % PG ND         2.02       0.96                                           TSS      64         1846       544                                            NO.sub.2 10         50         15                                             NO.sub.3 56         740        469                                            P        125        730        438                                            C1       1          31         18.5                                           F        ND         9          5                                              Sulfate  22         169        100                                            B        67         258        164.4                                          Cu       2.0        15.9       6.1                                            Fe       7.6        583        82.5                                           Al       1.8        71.3       13.7                                           Pb       1.5        136        25.6                                           Ca       1.5        34.1       9.13                                           K        234        1406       745                                            Mg       0.9        19.9       5.9                                            Mo       3.6        56.8       17.8                                           Na       676        2074       1420                                           Si       40.8       269.1      126.8                                          Sn       0.9        24.7       11.8                                           Zn       1.1        27.6       5.8                                            TTZ      130        370        242.7                                          Acetate  12         219        48.9                                           Glycolate                                                                              121        858        503                                            Formate  2          241        129                                            Benzoate 10         2590       385                                            EDTA     40         64         46                                             Oil      ND         1.0        0.03                                           ______________________________________                                         .sup.1 Low, High and Average Values (in ppm except where shown as wt. %)      are based upon thirty (30), 55 gallon antifreeze/coolant samples taken        from collection tanks at commercial antifreeze/coolant businesses in the      United States of America.                                                     .sup.2 Abbreviations have the following meaning: % EG = Weight Percent        Ethylene Glycol; DEG = Diethylene Glycol; PG = Propylene Glycol; NO.sub.2     = Nitrite; NO.sub.3 = Nitrate; Cl = Chloride; F = Fluoride; P =               Phosphorus; B = Boron; Cu = Copper; Fe = Iron; Al = Aluminum; Pb = Lead;      TTZ = Tolyltriazole; EDTA = Ethylene Diamine Tetracetic Acid; and Oil =       weight percent oil as an insoluble organic phase;#                            TSS = Total Suspended Solids (ppm; gravimetric analysis with 0.45 micron      filter); and ND = below detection limit of 2 ppm.                             .sup.3 Concentrations are in parts per million (ppm). All components are      given as total of soluble and insoluble forms.                           

In one embodiment the polyhydric alcohol- containing compositions aretaken from a heat exchange system, preferably the cooling system of aninternal combustion engine, and contains between about 5 weight percentand about 95 weight percent polyhydric alcohol, preferably ethyleneglycol, containing at least one heavy metal and typically containing anoil component. The instant process generally comprises the steps of:

(i) adjusting the pH of said polyhydric alcohol-containing compositionto between about 4.0 and about 7.5 by addition of an effective amount ofan pH adjusting agent to form a pH-adjusted composition; and

(ii) adding an effective amount of a precipitating agent for at leastone heavy metal and/or oil component present in the pH-adjustedcomposition.

In addition to the above steps the instant treatment process also mayinclude one or more of the following steps:

(iii) preferably also includes adding to the pH-adjusted composition ofstep (ii) an effective amount of a coagulating agent and an effectiveamount of a flocculating agent effective in forming a precipitatecontaining at least one heavy metal;

(iv) passing the pH-adjusted composition through a first filtrationmeans to remove a major amount of said heavy metal-containingprecipitate;

(v) passing the pH-adjusted composition after the first filtration meansthrough an organic separation means effective in removing organiccompounds (other than the polyhydric alcohol(s)) from the pH-adjustedcomposition;

(vi) passing the pH-adjusted composition from the first filtration meansthrough a second filtration means effective in the physical separationof particles of a smaller size that said first filtration means;

(vii) passing said pH-adjusted composition through a third filtrationmeans having an effective physical separation of particles by sizesmaller than said second filtration means; and

(viii) passing said pH-adjusted composition after filtration through anion exchanger (anion and/or cation) effective in the removal of at leastone solubilized heavy metal from said pH-adjusted composition.

Prior to addition of the precipitating agent the pH of the spentantifreeze/coolant is adjusted by addition of an effective pH-adjustingagent to adjust the effective pH to improve the precipitation of heavymetal(s) and is preferably adjusted to a pH between about 4.0 and about7.5 and more preferably between about 4.5 and 7.0. This pH adjustmentimproves the precipitation of heavy metals present in the spentantifreeze/coolant while concurrently adjusting the pH at a sufficientlyhigh pH so as to minimize acidic solubilization of heavy metalcompounds. The pH-adjusting agent may be any organic or inorganiccompound which effectively adjusts the pH to the selected pH, althoughit has been unexpectedly found that the use of nitric acid as thepH-adjusting agent in conjunction with the use of aluminum nitrate asthe precipitating agent provides unexpected results for precipitatingboth solubilized and insoluble lead species and for removing oilcomponents present in spent antifreeze/coolant from the cooling systemsof internal combustion engines. Organic acids, acidic organic salts,inorganic acids and acidic inorganic salts are employable herein beingeffective in adjusting the pH of the antifreeze/coolant. Representativeacids include nitric acid, phosphoric acid, sulfuric acid, hydrochloricacid, carboxylic acids, mixtures thereof and the like. It has beenobserved that salts useful as both pH-adjusting agents and/orprecipitating agents include the following representative acidic salts:the chlorides and nitrate salts of calcium, magnesium, zinc, aluminumand iron; the sulfate salts of magnesium, zinc, aluminum and iron; andthe like. It is beneficial to employ nitric acid as the pH-adjustingagent so as to prevent the introduction of corrosive anions and/oranions which may interfere with precipitation of heavy metals present inthe spent antifreeze/coolant during the pH adjustment step, although theconcurrent adjustment of pH and precipitation of heavy metal(s) with anacidic salt, e.g., preferably an aluminum nitrate hydrate such asAl(NO₃)₃ .9H₂ O, is within the scope of the instant invention.

The precipitating agent may be selected to provide for the formation ofheavy metal(s) precipitate in the pH-adjusted antifreeze/coolant. Theprecipitating agent need not result in the actual formation of a solidprecipitate if a coagulant and/or flocculant are to be employed but onlyneed render heavy metal(s) and/or oil present in the spentantifreeze/coolant susceptible to precipitation in the presence ofcoagulant and flocculant. When the precipitating agent is employedwithout the use of a coagulant and/or flocculant, it has been observedthat the rate of formation and separation of the precipitate may be tooslow for effective commercial use of the process, although the benefitsof instant process will nonetheless be achieved. The precipitating agentis added in an effective amount to precipitate a selected amount ofheavy metal(s) present in the spent antifreeze/coolant. Asaforementioned, the heavy metals most commonly found in spentantifreeze/coolant are lead (Pb from lead solder corrosion), iron (Fefrom water and radiator corrosion), zinc (Zn from metal corrosion andfrom zinc salts employed in antifreeze/coolants), copper (from radiatorcorrosion) and aluminum from corrosion (water pump, radiator, enginehead and engine block). It has been observed that the concentrations ofsolubilized lead and iron in a spent antifreeze/coolant are on the orderof up to about 100 parts per million (ppm) lead, and up to about 25 ppmiron, respectively. It has also been observed that insoluble leadcomponents may be present in concentrations up to about 150 ppm andinsoluble iron components may be present in concentrations up to about600 ppm. Typically total concentrations of lead and iron are set forthin Table A, hereinbefore. The effective amount of precipitating agentfor such concentrations of Pb and Fe will typically be between about 100ppm and about 6000 ppm (based upon use of Al(NO₃)₃.9H₂ O as theprecipitating agent) and preferably between about 500 ppm and about 5000ppm. The effective amount of precipitating agent employed is related tothe equivalents of heavy metal(s) to be precipitated and will varydepending upon the equivalents of the selected precipitating agentsuseful herein for forming heavy metal precipitates.

As aforementioned, selection of the precipitating agent may be from thatgroup of organic and/or inorganic compounds effective in the formationof a substantially insoluble species of at least one heavy metal presentin the spent antifreeze/coolant at the adjusted pH and may include saltsof heavy metal(s) such as phosphates, chlorides, sulfates, oxalates andthe like. The term "substantially insoluble" is meant to refer to aheavy metal species which will form as one or more precipitable speciesat a pH between about pH 4.0 and pH 7.5. Surprisingly, it has been foundthat use of aluminum nitrate (Al(NO₃)₃.9H₂ O) as a precipitating agentfor lead after pH adjustment (to between about 4.0 and about 7.5) of theantifreeze/coolant with nitric acid (as the pH-adjusting agent) isparticularly advantageous for use in formation of a lead precipitate andis also most beneficial for use in forming a precipitation with theadditional use of a coagulant and/or flocculant. The exact mechanism bywhich aluminum nitrate beneficially provides for formation of aprecipitate of lead is not fully understood but may relate to chemicalreaction with lead and/or may involve physical adsorption of leadspecies on the surface of aluminum, hydroxide or an aluminum oxide orother aluminum species formed in situ by addition of aluminum nitrate.

The selection of the coagulant and flocculant is correlated to thealcohol-based antifreeze/coolant being treated and is made to providefor effective precipitation and filtration of the precipitate andseparation of the precipitate by a mechanical filter. The coagulant maybe any of the well known commercially available coagulants includingCalgon 2466, Cyanamid 572C, mixtures thereof and the like. Theflocculant may be any of the well known commercially availableflocculants including PRIMAFLOC® C-3, MAGNIFLOC® 572C, Calgon 7736,Cyanamid 1820A, mixtures thereof and the like. Calgon POL-E-Z® 2466 is ahigh molecular weight, high charge cationic polyelectrolyte availablefrom Calgon Corporation. PRIMAFLOC® C-3 is a cationic polyelectrolyteflocculant characterized as a water-soluble polyamine (29-31%) and isavailable from Rohm and Haas Company. Calgon POL-E-Z® 7736 is a highmolecular weight, anionic polyelectrolyte available from CalgonCorporation. MAGNIFLOC® 572C (flocculant) is a very low molecularweight, liquid cationic flocculan available from American CyanamidCompany. Cyanamid 1820A is a cationic flocculant available from AmericanCyanamid Company. The selection of coagulants and flocculants forprecipitating solids in water based systems is well known as evidencedby the discussion in "The Nalco Water Handbook", Second Edition, (ISBM0-07-045872-3), 1988, at Part 2, Chapter 8 at pages 8.3 to 8.23,incorporated herein by reference.

In one embodiment the antifreeze/coolant is a spent antifreeze/coolantfrom the cooling system of an internal combustion engine, typically froman automobile or truck, having its pH adjusted to between about 4.5 andabout 7.0 with nitric acid as the pH-adjusting agent, followed bytreatment with an effective amount of aluminum nitrate as theprecipitating agent, followed by addition of coagulant, preferablyCalgon 2466, and flocculant, preferably Calgon 7736. The effectiveamount of coagulant is typically between about 75 ppm and about 300 ppm,preferably between about 150 ppm and about 225 ppm. The effective amountof flocculant is typically between about 25 ppm and about 300 ppm andpreferably between about 50 ppm and about 100 ppm. It has been observedthat there is an effective concentration range of coagulant andflocculant in the coagulant and flocculant solutions when such are to beadded to the antifreeze coolant after such has been treated with thepH-adjusting agent and the precipitating agent. Surprisingly, it hasbeen found that commercially available coagulants and flocculants aresold at concentrations significantly greater than beneficially suitablefor use in the instant process. For example, when treatment of alead-containing automotive antifreeze/coolant is effected with Calgon2466 as the coagulant and Calgon 7736 as the flocculant after theantifreeze/coolant has been treated with effective amounts of nitricacid and aluminum nitrate, it has been observed that the coagulant andflocculant as commercially available should be beneficially diluted fromits original commercial concentration by the addition of water or othersuitable solvent. For example, suitable dilution of coagulant Calgon2466 and flocculant Calgon 7736 for use in the instant invention may beprepared by mixing 100 parts (by weight or by volume) of the coagulantor the flocculant with water t o form up to 40,000 parts of coagulant orflocculant solution for use in the instant invention. The aforementionedwater diluted mixtures will preferably result in effectiveconcentrations of coagulant or flocculant in the resulting diluted watermixtures wherein the concentration of coagulant or flocculant is 0.25%to 5.0% of the concentration of the original commercial concentration ofthe coagulant or flocculant. Although the exact reason for thebeneficial effect obtained by use of a diluted coagulant or flocculantand the beneficial correlation of the concentration of the coagulant andflocculant to the antifreeze/coolant is not fully understood it has beenobserved that such may be related to the unique chemical environmentresulting from the use of an originally formulated ethylene-glycol basedantifreeze/coolant in the cooling system of an internal combustionengine and from localized concentrations of coagulant or flocculantresulting from the inherent difficulty in mixing large volumes ofliquids. The actual correlation in the concentration is believed toresult in an effective concentration of coagulant and flocculant, asdescribed above based upon the range of the heavy metals observed to bepresent in antifreeze/coolant removed from automotive cooling systems.

The antifreeze/coolant will form a solids phase (precipitate) and aliquid phase after treatment with the pH-adjusting agent andprecipitating agent and in a further embodiment preferably treatment asto coagulant and flocculant, as described above. The precipitate may beremoved by mechanical filtration. In addition, it has been observed thatproper agitation of the treated antifreeze/coolant enables skimming ofprecipitate from the top of the treated antifreeze/coolant as someportion of the precipitate is present at the surface of the treatedantifreeze/coolant. Further, it has been observed that recirculation ofthe spent antifreeze/coolant in the mixing tank by introduction of therecirculated stream above the surface of the antifreeze/coolant in themixing tank is beneficial in forming a precipitate suitable for skimmingas compared to the form of the precipitate formed when the recirculatedstream is introduced below the surface of the antifreeze/coolant in themixing tank. Accordingly, it is preferred to have a recirculation of thespent antifreeze/coolant in the mixing tank from below the surface ofthe antifreeze/coolant in mixing tank to a position sufficiently abovethe surface so as to expose the recirculated antifreeze/coolant to airwhereby some degree of contact with air occurs, such having beenobserved as effective in improving the form of the precipitate forskimming. This preferred recirculation is preferably commenced prior tothe addition of the p adjusting agent and precipitating agent. It hasbeen observed that the use of a process step wherein skimming of thesurface of the treated antifreeze/coolant is employed is beneficial inreducing the amount of precipitate which must be removed by filtration.This reduction in the amount of precipitate to be removed by filtrationboth increases the rate at which the treatment process may be carriedout and increases the useful life of the filtration means, thusdecreasing the number of times the filtration means must be replaced.The effective particle size removed by the filtration means will dependin part on whether a single or multiple filtration steps are to beemployed. If a single filtration step is to be employed the filteringmeans will preferably remove particles having a particle size greaterthan about 50 microns, although use of a single filtration step is notemployed. If this first filtration is the first filtration means in aseries of filtration means, then this first filtration means willpreferably be effective in the removal of particles having a particlesize greater than about 100 microns. In one embodiment it has been foundto be beneficial to employ at least three filtration steps wherein thefirst filtration means is effective in removing species larger thanabout 100 microns, a second filtration means effective in removingspecies larger than about 40 microns and a third filtration means isbeneficially employed wherein such is effective in removing specieslarger than about 5 microns. An optimal fourth filter may be employedwherein such fourth filtration means is effective in removing specieslarger than about 0.2 microns, preferably larger than about 0.1 microns.Mechanical filtration means having effective filtration sizes as abovediscussed are well known in the prior art. Optionally, as hereindescribed, an organic separation filter may be provided in conjunctionwith the previously discussed mechanical filters.

In a further embodiment, the treated, filtered, spent antifreeze/coolantis passed through an active filter for the removal of organic compounds,e.g., oils, aldehydes and organic acids. Representative of such activefilters are the various activated carbon filters sold under thetradename Fulflo™ by Parker Hannifin Corporation-Commercial FiltersGroup or a No. 2 Anthacite filter sold by Penfield Liquid Treatment. TheFulflo™ filter is characterized by its honeycomb filter structure havingan activated carbon surface while the Penfield filter is a looselypacked carbon filter. The active carbon filter acts as an organicseparation means effective in the selective removal of organic compoundsfrom the polyhydric alcohol/water mixture forming spentantifreeze/coolant.

It has been found beneficial to provide two or more filtration means forthe spent antifreeze/coolant (either before or after aforementionedorganic separation means) to effectively remove materials greater thanabout 5 microns, and more preferably to remove materials greater thanabout 0.2 microns. It has been found that the use of one or moreadditional mechanical filtration steps in conjunction with a firstfiltration means step is most advantageous in the separation of bulkyorganic and inorganic compounds and both large and small particulatesolids. Further, by providing a series of ever smaller size filters thelikelihood of clogging smaller pore filters with larger materials iseffectively eliminated. In one embodiment the process employs a firstfiltration means effective in removing materials greater than about 100microns, a second filtration means effective in removing materialsgreater than about 40 microns, a third filtration means effective inremoving materials greater than about 5 microns, and a fourth filtrationmeans effective in removing materials greater than about 0.2 microns.

In a further embodiment the instant process may also involve treatmentwith at least one ion-exchange resin to remove solubilized speciespresent in the spent antifreeze/coolant. A possible result of theinitial pH-adjustment of the instant process is the formation ofsolubilized cationic and/or anionic species of one or more heavy metals.The pH-adjustment to a pH between about 4.0 and about 7.5 is selected soto minimize the formation of such solubilized cationic and/or anionicspecies of such heavy metals, especially solubilized lead species.Although it has been observed that no such solubilized cationic species(less than the lowest measurement limit of 2 ppm), e.g., solubilizedlead, are present after the addition of the pH-adjustment agent,precipitating agent, coagulant and flocculant it is believed to bebeneficial to treat the filtered, spent antifreeze/coolant with a cationand/or anion exchange resin to assure that essentially no solubilizedheavy metal is present. It has also been observed that such ionexchangers also may act as filtration means for effectively removingmaterials having a size greater than about 2.0 microns. Further, sincesome solubilized species will pass through filtration means having apore size greater than 0.005 and remain as solubilized species it isbeneficial to employ an ion exchange material whereby such species areselectively removed by other than physical separation.

It is desirable to remove any solubilized heavy metals from the spentantifreeze/coolant so that such may be properly handled and properlydisposed. Accordingly, the filtered, spent antifreeze/coolant may betreated with a cation exchange and/or anion exchange resin effective inthe removal of solubilized heavy metal cation(s), or anions. Cationexchange resins useful in the removal of solubilized heavy metal cationsinclude well known cation exchange resins such as Rohm and Haas DP-1,Rohm and Haas Amberlite® IRC-718, Duolite® C-464, Purolite® C-106 andIonic® CNN. Rohm and Haas Amberlite® IRC 718 is preferred owing to itseffectiveness in the removal of solubilized lead and its cost.Amberlite® IRC 718 is a chelating cation exchange resin having a highaffinity for heavy metal cations over alkali or alkaline earth metals inthe pH range between about 4.0 and about 7.5 and is formed from DowChemical Company's SBR resin; a styrene-divinyl benzene material and isavailable from Rohm and Haas. Anion exchange resins which may beemployed herein include Rohm and Hass Amberlite® IRA 400; PuroliteA-600; Ionic® ASB-1; and Duolite®A-109. It has been observed that theuse of an anion exchange resin may not always be beneficial owing to thehigh concentration of anions present, present in the treatedantifreeze/coolant, e.g., nitrate, in the treated antifreeze.Nevertheless, there may be instances where an anion exchange resin maybe beneficially employed, e.g., where the anion exchange resin isselective to one or more anionic species. Further, it is well known thation exchange resins having both cation and anion exchangecharacteristics are commercially available and such dual exchange resinsmay be employed herein. For example the ion-exchange media of U.S Pat.No. 4,908,137, incorporated herein, is believed to be a novelion-exchange media useful herein in the removal of heavy metal ions.

The treatment with the cation and/or anion exchange resin ("ionexchange") may be accomplished after suitable mechanical filtration ofthe spent antifreeze/coolant after the addition of the pH-adjustingagent, precipitating agent, coagulant and flocculant has resulted inprecipitation of insoluble heavy metal compounds. Since the presence oflarge particulate matter will tend to clog most ion exchange materials,it is preferred that the ion exchange step follow a mechanicalfiltration step where particles having a size greater than about 5microns have been removed.

The reference to "filtration means" is meant to designate the variousfiltration devices hereto known in the prior art for use in the physicalseparation of materials (including both organic species and inorganicspecies) based on size. Filtration devices suitable for use in theinstant invention are commercially available. For example, the firstfiltration means of 100 microns and above may be a 3M Brand liquidfilter bag formed from polypropylene or stainless steel as described in3M sales brochure 70-0701-3209-0(201)iii 1989, incorporated herein. Thesecond filtration means having separation means of about 40 microns andabove may be a 3M Brand liquid cartridge filter having a pleatedpolypropylene design as described in 3M sales brochure70-0702-2790-8(201.5)11, incorporated herein.

In one embodiment the treatment with a cation exchange resin may bereplaced in part or in whole with treatment with an anion exchangeresin. In some instances the heavy metal(s) may be present or may beconverted into an anionic species. In some instances it may bebeneficial to treat the spent antifreeze/coolant to form an anionicspecies of the heavy metal, since in some instances its removal as ananionic species may be more effective than its removal as a cationicspecies. The formation of such anionic species may be beneficial owingto the desire to increase the reserve alkalinity of the spentantifreeze/coolant in preparation for its reprocessing into a workingantifreeze/coolant for use in an automotive cooling system.

The final composition obtained from the various embodiments of theinstant invention are characterized as having lower concentrations ofone or more heavy metal components and is typically characterized asbeing an aqueous composition(s) containing between about 5 and about 95weight percent polyhydric alcohol, preferably ethylene glycol, andcontaining less than about 5 ppm soluble lead, generally less than 2 ppmsoluble lead. These aqueous polyhydric alcohol compositions may beemployed in the manufacture of a working antifreeze by addition ofcorrosion inhibitors hereto employed in the manufacture of antifreeze/coolant compositions or may be employed for other common uses for thepolyhydric alcohol.

When the use is for antifreeze/coolant, such corrosion inhibitors willbe employed in effective amounts correlated to any residualconcentration of components of corrosion inhibitors present from thatpresent in the spent antifreeze/coolant which was not removed by theinstant process. For example, solubilized silica and nitrate may bepresent in the compositions derived from the instant process, since thevarious steps of precipitation, organics separation and mechanicalfiltration may not be effective in their complete removal. Chemicalanalysis of the treated spent antifreeze/coolant will provide a basisfor correlating the effective amount of corrosion inhibitor which shouldbe added to the treated aqueous antifreeze/coolant to form an effectiveworking antifreeze. In some instances the formation of a workingantifreeze may also require the addition of ethylene glycol or freshantifreeze or removal of water to obtain a solution having the desiredfreezing point. Removal of water from the aqueous ethylene glycol may beby distillation, extraction or other known separation means.

The various steps of the instant process may be carried out at aneffective temperature wherein the antifreeze/coolant is in a liquidstate and is preferably between about 18° C. to about 45° C. and at aneffective pressure, preferably between about 0.9 atm to about 1.1 atm,or such other temperatures or pressures as may improve the process.

It has been observed that it is not preferred to pass the precipitateformed by addition of the pH-adjusting agent, precipitating agent,coagulant and flocculant through a high shear mechanical pump, since ahigh shear mechanical pump tends to form particles of smaller size bymechanical shearing, thus making it more difficult to remove particleswith large size filters. Accordingly, it has been found that it ispreferred to place a pumping means after the first filtration step whichto provide a pulling action after the first filtration means oralternatively, provide a diaphragm or other low shearing type pump aheadof first filtration means. Representative of high shear pumps is aMOYNO® SP Pump (available from Robbins & Wyers, Inc.) and representativeof a low shear pump is a Twin Diaphragm Pump (available from the AROCorporation). It has also been observed that by employing skimming ofprecipitate from the surface of antifreeze/coolant in the vessel towhich the pH-adjusting agent, precipitating agent, flocculant andcoagulant are added that sufficient precipitate can be removed tosignificantly reduce the problems associated with high shear pumps.

The instant process may be carried out in a batch wise or,alternatively, in a continuous mode. When carried out in a batch mode,the process is conducted by placing a selected quantity of spentantifreeze/coolant in a vessel. The pH-adjusting agent and precipitatingagent are added followed by addition of the coagulant and flocculantwhereby a precipitate will be formed. The contents of the vessel arethen filtered by a first filtration means to remove the precipitate fromthe liquid phase. It has been found advantageous to minimize themechanical action on the precipitate during this first filtration stepso as to minimize the fraction of smaller size particles which form as aresult of mechanical abrasion. Such mechanical abrasion may be minimizedby manual mixing for about 5 minutes after all ingredients have beenadded during which time it may be advantageous to skim precipitate fromthe surface of the mixture. The pH-adjusted composition may then besequentially passed through one or more filtration means, organicseparation means, additional filtration means and ion exchange means.

The treated antifreeze/coolant may be suitable for use as a component ofa working antifreeze/coolant without further treatment or may bedistilled to remove water and/or organic component and, thus, provide ahigher content polyhydric alcohol solution. Alternately, the instantprocess is well suited to be carried out in a continuous manner basedupon the process steps employed in the batchwise process discussedabove.

The instant process may also be employed as a treatment step in anantifreeze/coolant change-over process where the treatedantifreeze/coolant is returned to the cooling system of an internalcombustion engine after the addition of inhibitors and other suitablechemicals. Processes wherein a treated antifreeze/coolant isreintroduced to an engine cooling system include U.S. Pat. Nos.4,149,574, Re. 31,274, 4,791,890 and 4,792,403; said patentsincorporated herein by reference. For example, in U.S. Pat. No.4,793,403 the instant process may be substituted for the second meansfor treating the removed coolant (see: column 3, line 11 to column 3,line 28). In one embodiment the instant process is employed as theintermediate treatment step in the process of copending U.S. Ser. No.200,347, filed May 31, 1988, entitled, "FLUSH AND FILL METHOD ANDAPPARATUS", incorporated herein by reference thereto. In such a processa first liquid (spent antifreeze/coolant) is removed from a coolingsystem through the radiator neck opening via an elongated hollow tube,treated according to the instant process and then reintroduced aftertreatment as the antifreeze/coolant (second liquid) into the coolingsystem via the radiator neck via an elongated hollow tube (the same or asecond hollow tube). The treatment step is according to the instantinvention and includes addition of appropriate chemicals to form aworking antifreeze/coolant. The process of U.S. Ser. No. 200,347eliminates the need to access the cooling system at more than onelocation and eliminates the need to cut hoses for access to the coolingsystem. In general, a process according to the instant invention used inconjunction with a process according to U.S. Ser. No. 200,347 comprisesflushing/filling an automotive cooling system containing anantifreeze/coolant first liquid using a flushing apparatus comprising incombination a pumping means, liquid switching means, an elongated hollowtubular member and an automobile having an automobile radiator having aneck opening and an over-flow container, said neck opening and saidover-flow container containing an antifreeze/coolant first liquid, to bereplaced with an antifreeze/coolant second liquid (comprising theantifreeze/coolant first liquid treated according to the instantinvention and then provided with an inhibitor package), wherein saidelongated hollow tubular member forms an elongated open fluid passagewayextending into the automobile radiator through said neck opening foraccessing said antifreeze/coolant first liquid, one end of the elongatedhollow tubular member adapted to engage a connecting means in a fluidtight relationship to connect the said elongated tubular member to saidpump means and switching means and for removing said first liquid andfor introducing said second liquid through said elongated hollow tubularmember to said automobile radiator, said process comprising:

a) removing at least a portion of the antifreeze/coolant first liquidfrom the automotive cooling system through said elongated hollow tubularmember using said pumping means connected to said liquid switchingmeans;

b) treating said first liquid according to the instant invention andadding thereto an inhibitor package to form an antifreeze/coolant secondliquid; and

c) introducing said antifreeze/coolant second liquid to said automotivecooling system through said elongated hollow tubular member using saidpumping means and switching means.

The instant process is beneficially carried out using a recycleapparatus comprising:

i) holding means for holding said spent antifreeze/coolant;

(ii) pH adjusting means for adjusting the pH of said spentantifreeze/coolant with a pH adjusting agent; and

(iii) addition means for adding a precipitating agent to said spentantifreeze/coolant.

In a further embodiment the recycle apparatus comprises:

(i) holding means into which a spent antifreeze/coolant may be placed;

(ii) pH adjusting means for adjusting the pH of the spentantifreeze/coolant in said holding means;

(iii) addition means for introducing into said holding means at leastone of a precipitating agent, a coagulant and a flocculant;

(iv) pumping means for removing the spent antifreeze/coolant from saidholding means;

(v) mechanical separation means for removing solids from said spentantifreeze/coolant based upon the size of said solids;

(vi) organic separation means for removing one or more components ofsaid spent antifreeze/coolant on the basis of chemical reaction,chemical adsorption or chemical absorption; and

(vii) ion exchange means effective in the removal by ion exchange of atleast one solubilized metal species in said spent antifreeze/coolant.

In this embodiment the recycle apparatus typically includes at leastitems (i), (ii), (iii), (iv) and (v) whereby the recycle apparatus iseffective in removing the precipitated solids in the holding means afteraddition of the pH adjusting agent and precipitating agent. Further, themechanical separation means may actually be one or more filterseffective in the removal of solids of various sizes, e.g., greater than100 microns or 40 microns or 5 microns.

The holding means may be a storage tank of conventional design withinlet and outlet ports for introduction of the original spent orrecirculated antifreeze/coolant and the treated antifreeze/coolant,respectively. A mechanical mixing or stirring means is typicallyemployed to mix the contents of the holding means. The pH adjustingmeans and addition means may be any liquid or dry addition apparatus forintroduction of the pH adjusting agent, precipitating agent, coagulantand/or flocculant. The pumping means may be any device effective intransferring the contents of the holding means to another process stepor to another storage area, including displacement by the force ofgravity. The mechanical separation means and organic separation meansmay be one or more filters as described in the instant application withreference to the instant process. The cation exchange means may be oneor more of the cation and anion exchange resins described herein.

In addition to the above recycle apparatus it has been observed that itmay be beneficial to employ skimming means and recirculating means incombination with the holding means, pH adjusting means and additionmeans. According to this embodiment the recycle apparatus comprises:

(i) holding means into which a spent antifreeze/coolant may be placed;

(ii) recirculating means for circulating spent antifreeze/coolant insaid holding means from a point below the surface of said spentantifreeze/coolant to a point above the surface of said spentantifreeze/coolant, whereby the recirculated spent antifreeze/coolantcontacts ambient air prior to its recirculation into said spentantifreeze/coolant;

(iii) pH adjusting means for adjusting the pH of the spentantifreeze/coolant in said holding means;

(iv) addition means for introducing into said holding means at least oneof a precipitating agent, a coagulant and a flocculant;

(v) skimming means for removing solids from the surface of said spentantifreeze/coolant in said holding means; and

(vi) may optionally contain one or more of mechanical separation means,organic separation means and ion exchange means, as discussed above.

EXAMPLES

The following examples are provided to further illustrate the inventionand are not intended to be limiting thereof. As employed in thefollowing examples the following abbreviations shall have the followingmeanings:

    ______________________________________                                        Wt. %:     Weight Percent                                                     EG:        Ethylene Glycol                                                    DEG:       Diethylene Glycol                                                  PG:        Propylene Glycol                                                   TTZ:       Tolyltriazole                                                      NO.sub.3 : Nitrate                                                            SO.sub.4 : Sulfate                                                            F:         Fluoride                                                           Cl:        Chloride                                                           EDTA:      Ethylene Diamine Tetracetic Acid                                   TSS:       Total Suspended Solids (ppm; gravimetric                                      analysis with 0.45 micron filter)                                  Oil:       Wt. % Oil as an insoluble organic phase.                           Elements are referred to by their chemical symbols,                           e.g., Al is aluminum, Pb is lead, and etc.                                    ml:        milliliter                                                         ND:        None Detected at 2 ppm or higher.                                  ______________________________________                                    

EXAMPLE 1

A spent antifreeze/coolant was obtained from commercialantifreeze/coolant change-over facilities and was from the coolingsystems of automotive and truck engines. The spent antifreeze/coolantwas treated according to the instant invention using the followingequipment in the order listed:

(1) Mixing Tank;

(2) 1/2" Diaphragm pump;

(3) 32" Bag Filter (3M 527A, 99.99 at 20 micron);

(4) 12" Bag Filter (McMaster Carr 5167K56, 100 micron);

(5) 20" Cartridge Filter (Pall RF400, 40 micron);

(6) 10" Activated Carbon (Filter Fulflo RC10, 10 micron);

(7) 20" Filter (3M 323A, 2 micron); and

(8) Cation Exchange Resin (Rohm and Haas Amberlite® IRC-718).

A 5125 gallon sample of the spent antifreeze/cooling was placed in themixing tank followed by the addition of 11.889 gallons of a 70 wt.percent nitric acid (remainder water). The contents of the mixing tankwere then mixed by a mechanical mixer for 20 minutes. To this mixturewas added 110.23 pounds of Al(NO₃.9H₂ O powder. This mixture was mixedfor 60 minutes. To this mixture was added 200 gallons of 0.5 weightpercent coagulant Calgon 2466 and 66.7 gallons of 0.5 weight percentflocculant Calgon 7736. The resulting mixture was then mixed for eighthours and filtered using the above noted filters in the order listed.

Tables I and II show the analysis of the spent antifreeze/coolant bothbefore and after treatment by the process of this invention. In Table I,the analysis of ethylene glycol, diethylene glycol and propylene glycolwas conducted by standard refractive index and gas chromotographicmethods, the oil percent was conducted by a gas chromotography, thetotal suspended solids were conducted by gravimetric analysis and allother analyses were conducted by High Pressure Liquid Chromatography("HPLC") analysis or Ion Chromatography ("IC"). Table II shows theresults of ICP analyses of several metals in their soluble and insolubleforms both before treatment and after treatment according to the instantinvention. In addition, the precipitate collected by the first 100micron filter bag was analyzed. Table I and Table II demonstrate theeffectiveness of the instant process in removing heavy metals,particularly lead, iron, copper, aluminum, magnesium, zinc and oil fromspent antifreeze/coolant compositions. Referring to Table I, it is shownthat in one embodiment of the instant process that after treatment theconcentrations of TTZ, BZT, oil, benzoate, glycolate and total suspendedsolids ("TSS") have been reduced. Referring to Table II, it is shownthat after treatment the soluble forms of aluminum, boron, calcium,iron, potassium, magnesium, molybdenum, phosphorus, lead, silicon andzinc are reduced. The insoluble forms of aluminum, boron, iron,magnesium, molybdenum, phosphorus, lead and zinc were reduced.

It is particularly important to note that after treatment according tothe invention that no soluble or insoluble lead was present in theantifreeze/coolant down to the detection limits of ICP analysis (about 2ppm) and, accordingly, is consistent with current and presentlypropossed regulations of the Environmental Protection Agency as being anon-hazardous material. Further, it has been observed that the form ofthe heavy metals in the precipitate is such that the heavy metals arenot leachable by water. Further, the precipitate contains various usefulmetal components and may be recycled for use as a component in cements,concrete, or used in other metal layered areas.

                  TABLE I                                                         ______________________________________                                        ANTIFREEZE/COOLANT COMPOSITION                                                BEFORE AND AFTER CHEMICAL TREATMENT                                           Analysis    Before Treatment                                                                           After Treatment                                      ______________________________________                                        pH          8.3          6.39                                                 EG, Wt %    53.0         48.1                                                 DEG, Wt %   2.0          1.9                                                  PG, Wt %    0.33         0.34                                                 TTZ, ppm    908          258                                                  BZT, ppm    114          ND                                                   NO.sub.2, ppm                                                                             92           115                                                  NO.sub.3, ppm                                                                             1029         4166                                                 Benzoate    3520         2896                                                 Oil, %      0.5          ND                                                   F, ppm      180          1.41                                                 Cl, ppm     137          141                                                  SO.sub.4, ppm                                                                             290          259                                                  Acetate     55           66                                                   Glycolate   820          660                                                  Formate     199          197                                                  Any acid, % 0.05         0.04                                                 TSS, ppm    509          19.0                                                 ______________________________________                                    

                  TABLE II.sup.1,2                                                ______________________________________                                        ANTIFREEZE/COOLANT COMPOSITION                                                BEFORE AND AFTER CHEMICAL TREATMENT                                                     SOLUBLE     INSOLUBLE                                               ELEMENT   FORM        FORM        PRECIPI-                                    NAME      Before  After   Before                                                                              After TATE                                    ______________________________________                                        Al        2.6     ND      6.1   ND    1340                                    B         434.8   303.6   23.7  3.2   1493                                    Ca        14.7    ND      6.7   ND    100.1                                   Fe        2.4     ND      23.6  ND    32.6                                    K         1206    986.6   ND    ND    789.5                                   Mg        8.1     ND      3.0   ND    30.6                                    Mo        48.5    20.5    ND    ND    ND                                      Na        2811    2308    65.0  30.9  2110                                    P         646.1   240.8   24.9  ND    95.8                                    Pb        3.0     ND      10.2  ND    11.5.sup.3                              Si        66.5    31.4    5.3   ND    15200                                   Zn        5.6     ND      5.4   ND    5.0                                     ______________________________________                                         .sup.1 Concentration in parts per million (ppm);                              .sup.2 ND means not detected at 2 ppm or higher                               .sup.3 EP Toxicity Testing (extractable lead) results were less than 0.1      ppm.                                                                     

EXAMPLE 2

Treatment of a spent antifreeze/coolant obtained from the coolingsystems of automotive and truck engines was treated according to theinstant invention using the following combination of equipment in theorder listed:

(1) 30 gallon tank;

(2)1/2" Diaphragm air pump;

(3) 12" 50 micron Bag Filter (McMaster Carr No. 5167K56);

(4) 20" 40 micron Cartridge (Pall No. RF400);

(5) 10" 10 micron Carbon Filter (Fulflo No. RC10);

(6) 20", 5 micron Cartridge Filter (Pall RF050); and

(7) 1.8 liter Cation Exchange Resin (Rohm and Haas Amberlite No.IRC-718)

A 10 gallon sample of a spent antifreeze/coolant was placed in the 30gallon mixing tank followed by the addition of 60 ml of 70 weightpercent nitric acid (remainder water). To this mixture was added 0.24pounds of Al(NO₃ 9H₂ O powder. This mixture was mixed for 15 minutes. Tothis mixture was added 1135.5 ml of 0.5 weight percent coagulant Calgon2466 and 378.5 ml 0.5 weight percent of flocculant Calgon 7736. Theresulting mixture was then mixed for 30 minutes and filtered using theabove noted filters in the order listed.

Table III shows an antifreeze/coolant and metals analysis of a spentantifreeze/coolant before treatment by the process of this invention.The analyses were conducted by ICP (Inductively Coupled Plasma)analysis. Tables IV and V show the result of ICP analysis of severalmetals and compounds in their soluble and insoluble forms both after atreatment step according to the instant invention. Tables IV and Vdemonstrate the effectiveness of the instant process in removing heavymetals, particularly lead and molybdenum, from spent antifreeze/coolantcompositions. Referring to Table V, it is shown that in one embodimentof the instant process that after treatment the concentrations of thesoluble forms of potassium, molybdenum, boron, iron, phosphorus andsilicon are reduced. The insoluble forms of aluminum, calcium, iron,magnesium, sodium, silicon, phosphorus, lead and zinc were reduced.Further, reference to Table IV demonstrates the ability of the instantprocess to remove TTZ and benzoate as well as reduce the total suspendedsolids in the treated antifreeze/coolant.

It is particularly important to note that after treatment according tothe invention that no detectable lead was present in theantifreeze/coolant down to the detection limits of ICP analysis (lessthan about 2 ppm). Further, since the antifreeze/coolant was passedthrough a 5 micron filter and the cation exchange resin (having aneffective filter size of 2.0 microns) the final treatedantifreeze/coolant meets current regulations of the EnvironmentalProtection Agency for being a non-hazardous material on the basis oflead content, (40 C.F.R. 261.24). Further, it has been observed that theform of the heavy metals in the instant precipitate is such that theheavy metals are not leachable by water.

                  TABLE III                                                       ______________________________________                                        A. ANTIFREEZE/COOLANT COMPOSITION                                             BEFORE CHEMICAL TREATMENT.sup.1                                               pH             9.42                                                           EG Wt %        32.2                                                           DEG Wt %       1.2                                                            PG Wt %        0.6                                                            Cl             25                                                             SO.sub.4       91                                                             TTZ            262                                                            NO.sub.2       ND                                                             NO.sub.3       472                                                            Benzoate       652                                                            TSS            650                                                            ______________________________________                                        .sup.1 Values are in micrograms per milliliter; ND means not detected         at 2 ppm or higher.                                                           ______________________________________                                        ELEMENT        AVERAGE.sup.1                                                  ______________________________________                                        B. SOLUBLE SPECIES BEFORE TREATMENT                                           Al             ND                                                             B              179.8                                                          Ca             ND                                                             Cu             ND                                                             Fe             11.5                                                           K              334.9                                                          Mg             ND                                                             Mo             9.7                                                            Na             1509.0                                                         P              464.0                                                          Pb             ND                                                             Si             70.7                                                           Sn             ND                                                             Zn             ND                                                             ______________________________________                                        .sup.1 Values are in ppm; ND means not detected at 2 ppm or                   ______________________________________                                        higher.                                                                       C. INSOLUBLE SPECIES BEFORE TREATMENT                                         Al             13.6                                                           B              9.9                                                            Ca             10.2                                                           Cu             ND                                                             Fe             80.7                                                           K              ND                                                             Mg             3.5                                                            Mo             ND                                                             Na             47.5                                                           P              24.9                                                           Pb             26.6                                                           Si             10.7                                                           Sn             ND                                                             Zn             7.4                                                            ______________________________________                                        .sup.1 Values are in ppm. ND means not detected at 2 ppm or higher.       

                                      TABLE IV                                    __________________________________________________________________________                                        AFTER                                                            AFTER        CATION                                    ELEMENT.sup.1                                                                          AFTER 50μ                                                                         AFTER 40μ                                                                         CARBON                                                                              AFTER 5μ                                                                          EXCHANGE                                  MEASURED FILTER FILTER FILTER                                                                              FILTER RESIN                                     __________________________________________________________________________    Wt % EG (GC)                                                                           28.3   28.5   28.3  28.5   28.5                                      Wt % EG (RI)                                                                           29.9   30.0   29.8  30.0   30.0                                      pH       6.7    6.8    6.7   6.8    7.9                                       Wt % DEG 1.05   1.02   0.98  0.99   0.96                                      Wt % PG  0.51   0.51   0.51  0.48   0.51                                      F        76     74     75    76     77                                        Cl       23     23     23    23     25                                        SO.sub.4 96     97     98    97     107                                       TTZ      206    235    90    101    61                                        NO.sub.3 3141   3017   2759  3103   3105                                      BENZOATE 325    318    250   232    247                                       TSS/PPM  456    112    68    36     24                                        __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________           AFTER 50  AFTER 40  AFTER     AFTER 5 MICRON                                                                          AFTER CATION                          MICRON BAG                                                                              MICRON FILTER                                                                           CARBON    FILTER    EXCHANGE RESIN                 ELEMENT                                                                              SOL  INS  SOL  INS  SOL  INS  SOL  INS  SOL  INS                       __________________________________________________________________________    Al     ND   131.7                                                                              ND   11.7 ND   21.1 ND   3.2  ND   4.0                       B      155.8                                                                              16.8 161.8                                                                              9.7  162.3                                                                              10.7 156.3                                                                              8.6  147.2                                                                              11.6                      Ca     ND   6.8  ND   4.0  2.6  4.0  2.1  2.3  2.2  3.1                       Cu     ND   ND   ND   ND   ND   ND   ND   ND   ND   ND                        Fe     ND   32.2 ND   ND   ND   3.1  ND   ND   ND   ND                        K      499.5                                                                              23.3 513.1                                                                              ND   526.7                                                                              ND   509.6                                                                              ND   252.3                                                                              ND                        Mg     ND   2.0  ND   ND   ND   ND   ND   ND   ND   ND                        Mo     7.7  ND   8.1  ND   8.7  ND   8.3  ND   ND   ND                        Na     1414 73.2 1434 21.6 1495 27.1 1440 19.2 1962 29.3                      P      190.9                                                                              161.2                                                                              194.7                                                                              7.8  205.1                                                                              18.6 199.0                                                                              ND   202.0                                                                              ND                        Pb     ND   ND   ND   ND   ND   ND   ND   ND   ND   ND                        Si     34.7 11.8 35.4 12.2 34.8 3.9  33.9 3.0  33.7 6.5                       Sn     ND   ND   ND   ND   ND   ND   ND   ND   ND   ND                        Zn     ND   3.8  ND   ND   ND   ND   ND   ND   ND   ND                        __________________________________________________________________________

EXAMPLE 3

A spent antifreeze/coolant was obtained from a commercial establishmentin the business of changing over spent antifreeze/coolant fromautomobiles and trucks. A portion of spent antifreeze was treatedaccording to one of the following chemical treatments to demonstrate theeffect of changes in the pH-adjusting agent, precipitating agent,coagulant and flocculant on the treatment process. The coagulant in eachtreatment was Calgon 2466 and the flocculant was Calgon 7736. Thetreatment process was carried out and the analysis conducted as setforth, except as noted below in Example 2 for following ten (10)different chemical treatments and except the antifreeze/coolant samplesize which was treated was 500 milliliters.

    ______________________________________                                        TREAT-                                                                        MENT                                                                          NO.    CHEMICAL TREATMENT                                                     ______________________________________                                        1      The pH of the sample was adjusted to about                                    7.0 with organic acid (acetic acid-                                           CH.sub.3 COOH, 99.7% solution); by treatment                                  with 0.75 ml of organic acid followed by                                      addition of 1.3 grams of                                                      Al (NO.sub.3).sub.3.9H.sub.2 O, followed by addition                          of 30 milliliters (ml) coagulant (0.25%                                       volume) solution, and then followed by                                        addition of 10 ml. of 0.25% flocculant                                        solution.                                                              2      The pH of the sample was adjusted to about                                    7.0 with 1.9 grams of Ca(NO.sub.3).sub.2.2H.sub.2 O                           (without addition of any pH adjusting agent,                                  coagulant and flocculant).                                             3      The pH of the sample was adjusted to about                                    7.0 with 0.75 ml of inorganic acid (70 wt %                                   nitric acid, followed by treatment with 1.3                                   grams of Al(NO.sub.3).sub.3.9H.sub.2 O as the                                 precipitating agent and then followed by                                      addition of 30 ml of a 0.25% solution of the                                  coagulant.                                                             4      The pH of the sample was adjusted to about                                    7.0 with 0.75 ml of nitric acid solution (70                                  wt % HNO.sub.3), followed by addition of 1.3                                  grams Al(NO.sub.3).sub.3.9H.sub.2 O as a precipitating                        agent, followed by addition of a 10 ml of                                     0.25 wt % solution of the flocculant.                                  5      The pH of the sample was adjusted to about                                    7.0 with 0.75 ml, nitric acid aqueous                                         solution (70 wt % of HNO.sub.3); followed by                                  addition of 1.3 grams of Al(NO.sub.3).sub.3.9H.sub.2 O,                       followed by addition of 10 ml of a 0.25 wt %                                  aqueous solution of the flocculant, and then                                  followed by addition of 30 ml of a 0.25 wt %                                  solution (aqueous) of the coagulant.                                   6      The pH of the sample was adjusted to a pH of                                  about 7.0 by addition of 0.75 ml of aqueous                                   nitric acid (70 wt % HNO.sub.3), followed by                                  treatment with 1.3 grams Al(NO.sub.3).sub.3.9H.sub.2 O,                       followed by addition of 10 ml of a 0.25 wt %                                  solution coagulant, and then 30 ml of the 0.25                                wt % aqueous flocculant solution.                                      7      The pH of the sample was adjusted to about pH                                 7.0 with 0.75 ml aqueous nitric acid (70 wt %                                 HNO.sub.3); and then mixed with 1.3 grams                                     Al(NO.sub.3).sub.3.9H.sub.2 O followed by addition of 30                      ml of a 0.25 wt % aqueous solution of coagulant,                              and then followed by addition of 10 ml of a 0.25                              wt % aqueous solution of flocculant.                                   8      The pH of the sample was adjusted to about pH                                 7.0 with 0.75 ml of nitric acid (70% HNO.sub.3);                              followed by treatment with 1.3 grams                                          Al(NO.sub.3).sub.3.9H.sub.2 O followed by addition of 15                      ml of a 0.5 wt % solution of coagulant and then                               followed by addition of 5 ml of a 0.5 wt %                                    solution of the flocculant.                                            9      The pH of the sample was adjusted to about pH                                 7.0 by addition of 0.7 ml of an aqueous formic                                acid solution (88% Formic acid-HCOOH) followed                                by addition of 1.3 grams of Al(NO.sub.3).sub.3.9H.sub.2 O,                    followed by addition of 30 ml of a 25 wt %                                    aqueous solution of coagulant, and then                                       followed by addition of 10 ml of a 0.25 wt %                                  aqueous solution of flocculant.                                        10     The sample was treated with 30 ml of a 0.25                                   wt % aqueous solution of the coagulant and                                    with 10 ml of a 0.25 wt % solution of the                                     flocculant (comparative sample without                                        pH-adjusting agent and without precipitating                                  agent).                                                                ______________________________________                                    

Each of the above samples were then filtered through a 25 micron filterand the final treated antifreeze/coolant analyzed. The results of theanalyses are set forth in Table VI. Table VI demonstrates thatsurprising results obtained by use of the adjustment of the pH tobetween about 4.0 and about 7.5, use of a precipitating agent and theuse of several concentrations of coagulant and flocculant.

                                      TABLE VI                                    __________________________________________________________________________    TREATMENT NO.                                                                 CONTROL.sup.1                                                                             1    2    3    4    5    6    7    8    9    10                   __________________________________________________________________________    pH   9.1    5.87 7.5  5.54 5.18 5.39 5.41 5.55 5.25 5.13 9.1                  Al, ppm                                                                            15.9   ND   ND   ND   ND   ND   ND   ND   ND   ND   3                    B, ppm                                                                             146.2  125  147  127  125  125  121  127.4                                                                              130.6                                                                              129.4                                                                              128                  Ca, ppm                                                                            3.2    2.4  33.2 3.0  3.4  2.8  ND   2.8  3.5  ND   ND                   Fe, ppm                                                                            24.7   ND   ND   ND   ND   ND   ND   ND   ND   ND   3.0                  K, ppm                                                                             640.0  506  604  483  522  490  487  490.0                                                                              506.4                                                                              517.0                                                                              507.0                Mg, ppm                                                                            ND.sup.2                                                                             ND   ND   ND   ND   ND   ND   ND   ND   ND   ND                   Mo, ppm                                                                            16.7   12.3 12.8 11.9 12.4 12.1 ND   11.8 12.2 ND   13.3                 Na, ppm                                                                            1471   1319 1437 1366 1367 1331 1350 1295 1365 1426 1210                 P, ppm                                                                             444    142  61.9 139  137  140  136  141  147  139  331                  Pb, ppm                                                                            19.7   ND   ND   ND   ND   ND   ND   ND   ND   ND   2.8                  Si, ppm                                                                            109.3  44.7 55.2 44.5 45.9 39.8 ND   40.7 40.6 ND   42.0                 Zn, ppm                                                                            7.2    ND   ND   ND   ND   ND   ND   ND   ND   ND   ND                   __________________________________________________________________________     .sup.1 Antifreeze/Coolant prior to treatment as obtained from the cooling     systems of automobiles/trucks.                                                .sup.2 "ND" means not detected at 2 ppm or higher.                       

The results in Table VI demonstrate the adjustment of the pH and use ofthe precipitating agent (e.g. Treatment Nos. 6 and 9) followed byaddition of the coagulant and flocculant was more effective than use ofonly the coagulant and flocculant (e.g., Treatment No. 10), or by use ofonly Ca(NO₃)₂.2H₂ O as the precipitating agent (Treatment No. 2). When aprocess according to this invention is employed (as in Treatment Nos. 6and 9) it is observed that the treated solutions from Treatment Nos. 6and 9 have reduced concentrations of iron, molybdenum, silicon and zincbelow detection limits (2 ppm). Further, while both Treatments 6 and 9removed detectable solubilized lead, Treatment No. 10 (employing onlycoagulant and flocculant addition) gave a treated product containing 2.8ppm Pb, 3.0 ppm Fe, 3.0 ppm Al and 13.3 ppm Mo.

EXAMPLE 4

The process employed in example 3 (Treatment No. 7) was repeated using apropylene glycol-based antifreeze/coolant having the composition shownin Table VII. The propylene glycol-based antifreeze/coolant had beenemployed as the antifreeze/coolant in an automotive cooling system toprovide the "original used antifreeze/coolant" employed in the instantexample. The treatments with the pH-adjusting agent (HNO₃),precipitating agent (Al(NO₃)₃.9H₂ O), coagulant (Calgon 2466) andflocculant (Calgon 7736) were conducted as described in Example 3 toprovide a treated propylene glycol-based antifreeze/coolant as shown inTable VII, below. As shown in Table VII, the instant process waseffective in removing an amount of potassium, phosphorus and TotalSuspended Solids and from the original used antifreeze/coolant. Sincethe original used antifreeze/coolant did not contain several metals atdetection levels above about 2 ppm, the removal of these metals by theprocess of this invention could not be quantitatively evaluated.

                  TABLE VII                                                       ______________________________________                                        PROPERTIES OF ANTIFREEZE/COOLANT                                                      ORIGINAL USED       AFTER                                             TEST    ANTIFREEZE/COOLANT  TREATMENT                                         ______________________________________                                        pH      8.2                 6.1                                               PG, %   52.5                49.8                                              TTZ     28                  26.0                                              Benzoate                                                                              ND                  ND                                                NO.sub.3                                                                              803                 3700                                              SO.sub.4                                                                              171                 152                                               F       80                  66                                                Cl      50                  50                                                TSS     238                 14                                                Al, ppm ND                  ND                                                B, ppm  367.1               307.4                                             Ca, ppm ND                  ND                                                Cu, ppm ND                  ND                                                Fe, ppm ND                  ND                                                K, ppm  94                  59.5                                              Mg, ppm ND                  ND                                                Mo, ppm ND                  ND                                                Na, ppm 2083                1759                                              P, ppm  749.8               285.4                                             Pb, ppm ND                  ND                                                Si, ppm 57                  48.8                                              Sn, ppm ND                  ND                                                Zn, ppm ND                  ND                                                ______________________________________                                    

We claim:
 1. A process for the treatment of an aqueous compositioncontaining between about 5 weight percent and about 95 weight percent ofa polyhydric alcohol, having a pH and containing at least one heavymetal wherein said process comprises:(i) adjusting the pH of saidaqueous composition to a pH between about 4.0 and about 7.5 by additionof an effective amount of a pH adjusting agent to form a pH-adjustedcomposition and adding thereto of an effective amount of a precipitatingagent for said heavy metal wherein said precipitating agent is selectedfrom the group consisting of organic salts,, inorganic salts andmixtures thereof.
 2. A process according to claim 1 wherein said processcomprises the following additional steps:(ii) adding to the pH-adjustedcomposition an effective amount of coagulating agent and an effectiveamount of a flocculating agent to form a precipitate containing at leastone heavy metal; and (iii) passing the pH-adjusted composition through afirst filtration means to remove heavy metal-containing precipitate fromsaid pH-adjusted composition.
 3. A process according to claim 2 whereinsaid process comprises the following additional steps:(iv) passing saidpH-adjusted composition of step (iii) through a second filtration meanscapable of removing species greater than about 40 microns; (v) passingthe pH-adjusted composition from step (iv) through an organic separationmeans effective in removing organic compounds other than said polyhydricalcohol form said pH-adjusted composition; (vi) passing said pH-adjustedcomposition through a third filtration means capable of removing speciesgreater than about 0.2 microns; and passing said pH-adjusted compositionof step (vi) through ion exchange means effective in the removal of atleast one solubilized heavy metal present in said pH-adjustedcomposition.
 4. A process according to claim 3 wherein said processcomprises the following additional steps:(viii) passing said pH-adjustedcomposition of step (vii) through water removal means whereby betweenabout 10 weight percent and about 100 weight percent of said water isremoved from said pH-adjusted composition.
 5. A process according toclaim 4 wherein said water removal means are distillable means.
 6. Aprocess according to claim 1 or claim 2 or claim 3 or claim 4 whereinsaid aqueous composition is a heavy metal-containing polyhydricalcohol-containing antifreeze/coolant taken from the cooling system ofan internal combustion engine.
 7. A process according to claim 6 whereinsaid polyhydric alcohol is ethylene glycol.
 8. A process according toclaim 7 wherein said ethylene glycol is present in an amount of between30 and 70 volume percent.
 9. A process according to claim 6 wherein saidpH of said aqueous composition is between about 8.2 and about 10.0. 10.A process according to claim 1 or claim 2 or claim 3 or claim 4 whereinthe pH-adjusting agent is at least one pH-adjusting agent selected fromthe group consisting of organic acids, inorganic acids, acidic organicsalts, acidic inorganic salts and mixtures thereof.
 11. A processaccording to claim 10 wherein the pH-adjusting agent is selected fromthe group consisting of nitric acid, phosphoric acid, sulfuric acid,hydrochloric acid, carboxylic acids and mixtures thereof.
 12. A processaccording to claim 11 wherein said pH-adjusting agent is nitric acid.13. A process according to claim 1 or claim 2 or claim 3 or claim 4wherein said precipitating agent is selected from the group consistingof chlorides, sulfates, phosphates, aluminum nitrates and mixturesthereof.
 14. A process according to claim 2 or claim 3 or claim 4wherein the flocculating agent is an anionic flocculant.
 15. A processaccording to claim 2 or claim 3 or claim 4 wherein the coagulating agentis a cationic coagulating agent.
 16. A process according to claim 2 orclaim 3 or claim 4 wherein the flocculating agent is an anionicflocculant and the coagulating agent is a cationic coagulating agent.17. A process according to claim 2 or claim 3 or claim 4 wherein saidcoagulant is present in an amount between about 75 ppm and about 300 ppmand said flocculant is present in an amount between about 25 ppm andabout 300 ppm.
 18. A process according to claim 2 or claim 3 or claim 4wherein said aqueous composition is obtained from a cooling system of aninternal combustion engine, contains 5 volume percent to 95 volumepercent ethylene glycol, contains up to about 150 ppm lead, saidpH-adjusting agent is nitric acid, said precipitating agent isAl(NO₃)₃.9H₂ O, said coagulant is present in an amount between about 75ppm and about 300 ppm, said flocculant is present in an amount betweenabout 25 ppm and about 300 ppm.
 19. A process according to claim 1 orclaim 2 or claim 3 or claim 4 wherein said pH-adjusted compositioncontains less heavy metal than said aqueous composition after additionof said precipitating agent.
 20. A process according to claim 1 or claim2 or claim 3 or claim 4 wherein said process is carried out at aneffective temperature between about 18 degrees Centigrade and about 45degrees Centigrade and at an effective pressure between about 0.9 atmand about 1.1 atm.
 21. A process according to claim 1 or claim 2 whereinthe pH in step (i) is adjusted to between about 4.5 and about 7.0.
 22. Aprocess according to claim 2 wherein said first filtration means iscapable of removing species greater than about 100 microns.
 23. Aprocess according to claim 1 or claim 2 or claim 3 or claim 4 whereinsaid polyhydric alcohol is selected from the group consisting ofethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, glycerol, butene glycol, the monoethylether of glycerol, thedimethyl ether of glycerol, alkoxy alkanols and mixtures thereof.
 24. Aprocess according to claim 23 wherein said polyhydric alcohol isselected from the group consisting of ethylene glycol, diethyleneglycol, propylene glycol and mixtures thereof.
 25. A process accordingto claim 1 wherein said process comprises the following additionalstep:(ii) adding to the pH-adjusted composition of step (i) an effectiveamount of a coagulating agent.
 26. A process according to claim 1wherein said process comprises the following additional step:ii) addingto the pH-adjusted composition of step (i) an effective amount of aflocculating agent.
 27. A process according to claim 1 wherein saidprocess comprises the following additional step:(ii) passing saidpH-adjusted composition of step (i) through filtration means.
 28. Aprocess according to claim 1 wherein said process comprises thefollowing additional step:(ii) adding to said pH-adjusted composition ofstep (i) an effective amount of a coagulating agent and an effectiveamount of a flocculating agent to form a precipitate containing at leastone heavy metal.
 29. A process according to claim 1 wherein said processcomprises the following additional step:(ii) contacting saidpH-adjusting composition of step (i) with air.
 30. A process accordingto claim 29 wherein said process comprises the following additionalstep:(iii) skimming heavy metal containing precipitate from the surfaceof said pH adjusted composition.
 31. A process for the treatment of anaqueous composition containing between about 5 weight percent and about95 weight percent of a polyhydric alcohol wherein said aqueouscomposition is an antifreeze/coolant taken from the cooling system of aninternal combustion engine having a pH and containing at least one heavymetal wherein said process comprises:(i) removing saidantifreeze/coolant from said cooling system and then adjusting the pH ofsaid aqueous composition to between about 4.0 and about 7.5 by additionof an effective amount of an pH adjusting agent to form a pH-adjustedcomposition and adding thereto an effective amount of a precipitatingagent for said heavy metal.
 32. A process according to claim 31 whereinsaid process comprises the following additional steps:(ii) adding to thepH-adjusted composition an effective amount of coagulating agent and aneffective amount of a flocculating agent to form a precipitatecontaining at least one heavy metal; and (iii) passing the pH-adjustedcomposition through a first filtration means to remove heavymetal-containing precipitate from said pH-adjusted composition.
 33. Aprocess according to claim 32 wherein said process comprises thefollowing additional steps of:(iv) passing said pH-adjusted compositionof step (iii) through a second filtration means capable of removingspecies greater than about 40 microns; (v) passing the pH-adjustedcomposition from step (iv) through an organic separation means effectivein removing organic compounds other than said polyhydric alcohol formsaid pH-adjusted composition; (vi) passing said pH-adjusted compositionthrough a third filtration means capable of removing species greaterthan about 0.2 microns; and (vii) passing said pH-adjusted compositionof step (vi) through ion exchange means effective in the removal of atleast one solubilized heavy metal present in said pH-adjustedcomposition.
 34. A process according to claim 33 wherein said processcomprises the following additional steps:(viii) passing said pH-adjustedcomposition of step (vii) through water removal means whereby betweenabout 10 weight percent and about 100 weight percent of said water isremoved from said pH-adjusted composition; and (ix) skimming a portionof said precipitate from said final pH adjusted composition of step (i).35. A process according to claim 34 wherein said water removal means aredistillation means.
 36. A process according to claim 32 or claim 33wherein said pH-adjusted composition contains less than 2 ppm lead afterremoval of said heavy metal precipitate.
 37. A process according toclaim 31 or claim 32 wherein said polyhydric alcohol is selected fromthe group consisting of ethylene glycol, diethylene glycol, propyleneglycol, dipropylene glycol, glycerol, butene glycol, the monoethyletherof glycerol, the dimethyl ether of glycerol, alkoxy alkanols andmixtures thereof.
 38. A process according to claim 37 wherein saidpolyhydric alcohol is ethylene glycol.
 39. A process according to claim37 wherein said ethylene glycol is present in an amount of between 5 and95 volume percent.
 40. A process according to claim 37 wherein saidpolyhydric alcohol is propylene glycol.
 41. A process according to claim31 or claim 32 wherein the pH in step (i) is adjusted to between about4.5 and about 7.0.
 42. A process according to claim 41 wherein said pHof about said aqueous composition is between 8.2 and 10.0.
 43. A processaccording to claims 31 or claim 32 wherein the pH-adjusting agent is atleast one pH-adjusting agent selected from the group consisting oforganic acids, inorganic acids, acidic organic salts, acidic inorganicsalts and mixtures thereof.
 44. A process according to claim 43 whereinsaid pH-adjusting agent is at least one pH-adjusting agent selected fromthe group consisting of inorganic acids, acidic organic salts, acidicinorganic salts and mixtures thereof.
 45. A process according to claim43 wherein the pH-adjusting agent is selected from the group consistingof nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, andmixtures thereof.
 46. A process according to claim 31 or claim 32wherein said precipitating agent is selected from the group consistingof organic salts, inorganic salts and mixtures thereof.
 47. A processaccording to claim 46 wherein said precipitating agent is selected fromthe group consisting of chlorides, sulfates, phosphates, nitrates andmixtures thereof.
 48. A process according to claim 32 wherein theflocculating agent is an anionic flocculant.
 49. A process according toclaim 32 wherein the coagulating gent is a cationic flocculant.
 50. Aprocess according to claim 31 or claim 32 wherein said pH of saidaqueous composition is between about 8.2 and about 10.0.
 51. A processaccording to claim 50 wherein said aqueous composition is a heavymetal-containing ethylene glycol-containing antifreeze/coolant takenfrom the cooling system of an internal combustion engine.
 52. A processaccording to claim 32 wherein said coagulant is present in an amountbetween about 75 ppm and about 300 ppm and said flocculant is present inan amount between about 25 ppm and about 300 ppm.
 53. A processaccording to claim 31 or claim 32 wherein said aqueous composition isobtained from a cooling system of an internal combustion engine contains5 volume percent to 95 volume percent ethylene glycol, contains up toabout 150 ppm lead, said pH-adjusting agent is nitric acid, saidprecipitating agent is Al(NO₃)₃.9H₂ O.
 54. A process according to claim31 or claim 32 wherein the treated pH-adjusted composition contains lesssoluble lead as compared to the untreated pH-adjusted composition.
 55. Aprocess according to claim 31 wherein said process comprises thefollowing additional step:(ii) adding to the pH-adjusted composition ofstep (i) an effective amount of a coagulating agent.
 56. A processaccording to claim 31 wherein said process comprises the followingadditional step:(ii) adding to the pH-adjusted composition of step (i)an effective amount of a flocculating agent.
 57. A process according toclaim 31 wherein said process comprises the following additionalstep:(ii) adding to said pH-adjusted composition of step (i) aneffective amount of a coagulating agent and an effective amount of aflocculating agent to form a precipitate containing at least one heavymetal.
 58. A process according to claim 31 wherein said processcomprises the following additional step:(ii) contacting saidpH-adjusting composition of step (i) with air.
 59. A process accordingto claim 58 wherein said process comprises the following additionalstep:(iii) skimming heavy metal containing precipitate from the surfaceof said pH adjusted composition.